Process of hydrogenation.



C. ELLIS.

PROCESS OF HYDROGENATION. APPLIQATION FILED MAR-29,1912; RENEWED SEPTAILIQIG.

1,217,1 18. v Patented Feb.-20,1917.

" I 7 INVL'NTOR R Q a. 75. w v

UNITED STATES PATENT OFFICE.

CARLETON ELLIS, 0E MoNToLAIE, NEW JERSEY.

PROCESS 0E HYDROGENATION.

Specification of Letters Patent.

Application filed mareirae', 1512, Serial No. 686,988.

To all whom it may concern:

Be it known that I, CARLE'roN ELLIS, a citizen of the .United States,and a resident of Montclair, in the county of ,Essex and State of NewJersey, have invented certain new and useful Improvements in Processesof Hydrogenation, of which the following is a specification. a r

This invention relates to a process of treating organic materials,especially unsaturated fats, fatty acids and glycerids and similarmaterial, by ineans of hydrogen or hydrogen-yielding material, for thepur- I pose of'saturating such unsaturated bodies to a greater or lessextent.

This application is a division of -my former co-pending application,Serial No. 656,100, filed October 23, 19171, now Letters 1 Patent No.1,026,156 especially as regards oil colloids or colloidal catalyzers, asWell as those catalyzers formed, for example, in sitaby thermaldecomposition. This application also contains matter derived from-Serial No. 67 9,77 l filed February 24, 1912,

especially as regards the use of carbonaceous material in catalyticprocesses. Among the materials which may be treated in accordance withmy invention are their oxids, carbids, silicids, etc.

fatty acids asoleic or linoleic acids, or fatty acid mixtures, alsoglycerids as oleinsand linoleins including glycerlds such as cottonseed,castor, linseed, Chinese wood, Perilla, soy bean, corn, pea-nut, andfish oils.

The process of saturation is carried out with the aid ofcatalytic-material including such catalysts as coba lt,.nickel, copper,iron, palladium and platinum; also under certain circumstances chromium,manganese, titanium, molybdenum, vanadium, thorium, zir- 'conium,selenium, arfi tellurium preferably in a finely dividedstate; in so faras these may be adapted as hydrogenating catalystsunder the particularconditions imposed. Likewise under certain circumstances these elementsmay be employed in the form of Other compounds of silica are somewhatuseful,

' especially colloidal silica and nickel in admixture or combination.Carbon in its various forms and particularly charcoal may be used.

The fatty material and the like may carry catalytic material such as thebodies above mentioned, which,'if desired, may be employed in anoilsoluble or in a colloidal form. Metallo-organic compounds more orPatented Feb. 20, 1917. Renewed September 11, 1916. Serial No. 119,408.

less soluble in oil and consisting of or containing a metal unitedto anorganic radical such as the weak organic acid, as, for example, oleicacid, are useful to this end;

especially as by properly regulating conditions, such as, thetemperature, these metalloorganic compounds may be decomposed in apredetermined manner, setting free the catalyst, not necessarily as apulverulent catalyzer 1n the ordinary sense of the term,

but as an oil-colloid ina state of extreme subdivisiomand oftencolloidally dissolved or existing more or less in a state ofquasisolution' wonderfully conducive to accelerated terial and the'like.

hydrogen absorption by the fatty sma When such an oilcolloid is to loeproduced by heating an oil soluble met'allo-organio compound to therequisite temperature, the

selection .of the metallo-organic compound preferably applied, should bemade with particular reference to the hydrogen absorpconsidered, of theof hydrogenation to a-temperature above which the soap cannot exist assuch, or if formed, immediately decomposes so that the catalyzer doesnot enter into solution to any undesired extent. By holding the materialat a temperature about 10 C. above the decomposition point, undesirableformation of metallic soaps or metallo-organic bodies is prevented. Thistemperature, moreover, varies with the organic body under treatment, andpreferably is determined by formingin any suitable manner theme'tallo-organic compound and then gradually heating until thedecomposition point is'reached This temperature may thus establish theconditions governing the procedure with respect to the material in hand.

As anillust'rative example, a metallo-organic compound such as nickeloleate may be heatedwith an oil such for instance as cottonseed oilpreferably employing only a fewper cent. of the nickel compound and "thetemperature is maintained at about 200? (3., or if the oil will bearheating to a higher temperature without undesirable discoloration thenthe temperature may be raised somewhat higher and hydrogen is contactedwith the mixture as by bubbling the gas 1 through a body of same.Decomposition of the said nickel compound ensues and catalytic materialforms resulting in due course in the addition of hydrogen to theunsaturated bodies with which the thusformed catalyzer may come. intocontact.

gage.

In the accompanying diagrammatic drawings, an illustrative form oftreating apparatus which may be employed hereunder is shown in elevationwith a portion of one tower shown in section. In the drawing 1 and 2 arecontainers or towers of considerable height. These towers may if desiredbe packed with granular material of a nonmetallic nature, such forexample, as gran ules of charcoal, or if desired, with non-' metallicmaterial carrying or retaining a metallic catalyzer, the non-metallicmaterial being active or inactiv e as the case may be. Thetowers havebafiies' in some cases and as shown at 3, the bafiles have a lip Steammay be passed. A pipe 7 leads from the lower part, of the tower 1 to theupper 4 part of the tower 2 and serves to convey hydrogen gas from thelatter to the former, An oil main runs from the top of the tank 2 to thebottom of the tank 1. Hydrogen is generated in the electrolytic cell, 22and is forced by the pump 21 into the purifiers 19 and 17, then passesinto the tower 2 moves upwardly therethrough and then is forced into thetower 1 where it travels upwardly in the same manner coming in intimatecontact with the oil which is flowing in the opposite direction andbeing heated and if needful compressed to the] point required for themost effective reaction. Finally any residual gases discharging at 4'may be taken back to thepump 21 and used again. in the system in so, faras they may containany useful hydrogen content.

The oil entering at 5 with or without a colloidal or finely dividedcatalyzer is forced downwardly through the tower 1 and then forced intothe tower 2 under a pressure suflicient to ---enable the oil to movefreely against the pressure of the hydrogen gas. The oil dischargingfrom the bottom of the tower 2 is usually fully treated, that is to say,has been given the requisite/ addition of hydrogen, but this depends ofcourse, an the height of the towers and the pressure and othercircumstances, so that in case the oil isnotsufiiciently treated by onepassage through the apparatus it may ;'be passed through a second time,or as manytimes' as desired throughthe tower.

A composite catalyzer system may be employed, as for instance, in thatone tower or one portion of the tower a metallic catalyzer such asnickel may be employed while in another tower or in some portion of thesame tower, a catalyzer such as platinum or .palladium may be used. Orit may be found useful under certain conditions to have a metalliccatalyzer for one stage of the hydrogenation and a non-metalliccatalyzer for another stage of the operation and this may beaccomplished, for example, by layers of catal'yzers usually placedeither in the same tower or situatedor maintained in separate towers.

It should, however, be understood 'that the foregoing description ofapparatus and the procedure therewith is set forth purely forillustratiye. purposes and that the essence of the present inventionprescribes no limitations respecting the means suited for the'carryingout thereof.

The treatment of oil containing colloidal catalyst .in the condition ofa fog is not specifically claimed herein, the same being claimed in mycopending application 57 ,094

filed Oct. 21, 1915. The circulation and reuse of the unabsorbedhydrogen, after treatment of oil and catalyst therewith is not claimedherein, but inthe application above specified and in my copendingapplication 695,206 filed May 4, 1912 and in my copending application75,769 filed Feb. 2,

1916. The use of silicon-containing catalyst as herein described is notclaimed herein, but in my copending application 873,507 filed Nov. 23,1914. The colloidal catalyst and the preparation of the same are notclaimed herein but in my copending applications 50,462 filed Sept. 13,1915 and 89,093 filed Apr. 5, 1916. The hydrogenation of the unsaturatedconstituents with a catalyst at particularly described temperatures ca-Pable of producing stated efiects is claimed in my copendingapplication's 84,698" filed hgarch 1.6, 1916 and 86,522 filed March 24,1 6.

What I claim is: 1. In the process of hydrogenating oily material andthe like the step which comprises developing a finely divided catalyzerin a body of non-aqueous menstruum in liquid condition and in contactingsaid material with a hydrogen-containing gas in the presence of saidcatalyzer.

2. In the process of hydrogenating oily Y material and the like the stepwhich comprises developing a finely diyided catalyzer".

in an oily body in a liquid condition and a in contacting said materialwith a hydrogencontaining'gas in the presence of sald catalyzer.

3. In the process f hydrogenating oily material and the like the stepwhich com-.

I hydrogen-containing gas said catalyzer.

prises forming a finely divided catalyzer by thermal decomposition in anoily body in a liquid condition and in contacting said materlal with ahydrogen-contammg gas 1n thepresenceof said catalyzer.

A. In the process of hydrogenatingoily material and the like the stepwhich comprises forming a finely-divided catalyzer by. thermaldecompositionof a non-,Volatile decomposable nickel body in an oily bodyand in contacting said material with a hydrogencontaining gas in thepresence of said catalyzer. f

5. In the process of hydrogenati ng oily material and the like the stepwhich comprises forming'a. finely-divided catalyzer by thermaldecomposition of a decomposable nickel salt in an oily body and incontacting said material with a hydrogen-containing gas in the presenceof' said catalyzer.

6. In the process of hydrogenating oily material and the like the stepwhich comprises forming a finely-divided catalyzer by thermaldecomposition of a decomposable organic nickel salt in an oily body andin contacting said material with a hydrogen- 0 containing gas in thepresence of said catalyzer.

7. In the process of h-ydrogenating oily material and the like the stepwhich comprises forming a finely-dividedcatalyzer by thermaldecomposition of a decomposable nickel salt of afatty acid in an oilybody and in contacting said material with a 8. In the process ofhydrogenating oily material and the like the step which comprisesforming a .finely-divi'ded catalyzer' by thermal decomposition of nickeloleate in an oily body and in contacting said material with ahydrogen-containing gas in the presence of said catalyzer.

9. In the process of hydrogenating fatty material containing unsaturatedbodies the step which'comprises forming a finely-divided catalyzer bythermal decomposition of a potential catalyst comprising a decomposableorganic salt of a heavy metal in a liquid medium and in contacting saidfatty materialwith a hydrogen-containing gas.'-in the presence of saidcatalyzer.

10. In the process of hydrogenating oily material and the like the stepwhich comprises forming a finely-divided catalyzer by thermaldecomposition of a decomposable nickel salt and in contacting saidmaterial in the presence of with a hydrogen-containing gas in the'presence of said catalyzer. f I

11. In the process of hydrogenating oily' f material and the like thestep which comprises forming a finely-divided catalyzer by thermaldecomposition of a decomposable organic nickel salt and in contactingsaid material with a hydrogen-containing gas in the presence of saidcatalyzer. I

12. In the process of hydrogenating oily material and the like the step.which comprises forming a finely-dividedrcatalyzer by thermaldecomposition of a decomposable nickel salt of a fatty'acid and incontacting said material with a hydrogen-containing gas in the presenceof said catalyzer.

13. In the process of hydrogenating oily material and the like the stepwhich comprises forming a finely-divided catalyzer by I thermaldecomposition of nickel oleate and in contacting said material with ahydrogen-containing gas in the presence of said catalyzer.

14. In the process of hydrogenating fatty 'material containingunsaturated bodies the 's'te' which comprises forming a finelyl-divi edcatalyzer by thermal decomposition of a potential catalyst comprising adecomposable organic salt of a heavy metaland i contacting said fattymaterial with a hydr gen-containing gas in the presence of saidcatalyzer.

15. In the process of hydrogenating oily material and the like the stepwhich comgas.

17; In the process of hydrogenatlng" ol'ly material and the like thestep which co'm' prises heating a compound comprising a metallicbodyunited'to an organic radical to a decomposing temperature in thepresence of a non-aqueous menstruum and in \prises heating'ametal-containing material contacting some portion at least of theprodnets of such decomposition with said oily material in the presenceof a hydrogen-containing gas.

18. In the process of hydrogenating oily material and the like the stepwhich comprises heating ,a compound comprising a base metal united to anorganic radical to a I decomposing temperature in the presence ofanon-aqueous menstruum and in contacting some portion at least of theproducts of such decomposition with said oily material in the presenceof a hydrogen-containing gas.

19. In the presence of hydrogenating oily material and the like the stepwhich comprises heating nickel united. to an organic radical to adecomposing temperature in the presence of a non-aqueous menstruum and Iin contacting some portion at least of the products of suchdecomposition with said oily material in the presence of ahydrogencontaining gas.

20. In the process of hydrogenating oily material and the like the stepwhich comprises forming a colloidal catalyzer in an oily body in aliquid condition and in contacting said material With ahydrogen-containing gas in the presence of said catalyzer.

21. In the process of hy drogenating oily material and the like the stepwhich com prises forming a finely divided colloidal catalyzer in a bodyof non-aqueous menstruum in a liquid condition and in contacting saidmaterial with a hydrogemcontaining gas in the presence of saidoatalyzer.

22. In the process of hydrogenating oils and the like the step whichconsists in subjecting an unsaturated oil to hydrogen in the presence ofa colloidal catalyzer.

235 In the process of hydrogenating oils and the like the step Whichconsists in subjecting an unsaturated oil to hydrogen in} the presenceof acatalyzer formed in said unsaturated oil. 24. .The process oftreating unsaturated oils which comprises subjecting same at atemperature of at least 150 C. to the action of hydrogen in the presenceof a colloidal catalyzer.

25. The process of treating organic material containing unsaturatedbodies which comprises passing said material through a bed of fragmentalmaterial in the presence of a colloidal atalyzer and ahydroggen-containing gas. I7

26. The process of hardening oils, which comprises treating the oil with'asuitable metallic salt and in the presence of hydrogen, said' metallicsalt being soluble in the oil treated.

hydrogen.

'27. The process of hardening oils, which comprises treating the oilwith a metallic salt of the product treated in the presence of I2-8.,The' process for the reduction of organic compounds by a reducinggas and by catalysis, .which consists in treating such a compound withan organic metal salt and a reducing gas, substantially as described.

29. The process for the reduction of organic compounds by hydrogen andby catalysis, which consistsin treating such a compound with an organicmetal salt and hydro gen, substantially as described.

30. The process for the reductionof or-.

ganic compounds by gas mixtures containing hydrogen and by catalysis,which con-' sists in treating such a compound with an organic metalsalt,,and gas mixtures containing hydrogen, substahtially'as described.

31. The process for the reduction of may acids by a reducing gas and by'catalysis, which consists in treating such an acid with an organic metalsalt and a reducing gas,

maintaining at a temperature between the approximate limits of 150 and200 C.

34. In the process ofhydrogenat1ng OllS and the like, the step whichconsists in sub jecting oily' material containing, as naturalconstituents,-unsaturated bodies to hydrogen in the presence of acatalyst comprising colloidal nickel, while said oily, material ismaintained at a temperature of about 170 C.

Signed at Montclair in the county of Essex and State of New Jersey this28th day of March A. -D. 1912.

- Witnesses:

THoMAs F. Rooms,

HENRY F. MULLER.

oA aLE'roN ELLIS.

